Fourier Transform Microwave Spectrum of Propene-3‑d 1 (CH2CHCH2D), Quadrupole Coupling Constants of Deuterium, and a Semiexperimental Equilibrium Structure of Propene

• Published in: The journal of physical chemistry. A, Molecules, spectroscopy, kinetics, environment, & general theory Vol. 121; no. 16; pp. 3155 - 3166
• Main Authors: Demaison, Jean, Craig, Norman C, Gurusinghe, Ranil, Tubergen, Michael J, Rudolph, Heinz Dieter, Coudert, Laurent H, Szalay, Péter G, Császár, Attila G
• Format: Journal Article
• Language: English
• Published: United States American Chemical Society 27.04.2017
• ISSN: 1089-5639; 1520-5215
• DOI: 10.1021/acs.jpca.7b01470

The ground-state rotational spectrum of propene-3-d 1, CH2CHCH2D, was measured by Fourier transform microwave spectroscopy. Transitions were assigned for the two conformers, one with the D atom in the symmetry plane (S) and the other with the D atom out of the plane (A). The energy difference between the two conformers was calculated to be 6.5 cm–1, the S conformer having lower energy. The quadrupole hyperfine structure due to deuterium was resolved and analyzed for both conformers. The experimental quadrupole coupling and the centrifugal distortion constants compared favorably to their ab initio counterparts. Ground-state rotational constants for the S conformer are 40582.157(9), 9067.024(1), and 7766.0165(12) MHz. Ground-state rotational constants for the A conformer are 43403.75(3), 8658.961(2), and 7718.247(2) MHz. For the A conformer, a small tunneling splitting (19 MHz) due to internal rotation was observed and analyzed. Using the new rotational constants of this work as well as those previously determined for the 13C species and for some deuterium-substituted species from the literature, a new semiexperimental equilibrium structure was determined and its high accuracy was confirmed. The difficulty in obtaining accurate coordinates for the out-of-plane hydrogen atom is discussed.